CN100343231C - Dipyrrolinone subunit compound, coloring agent containing said compound and its preparation method - Google Patents
Dipyrrolinone subunit compound, coloring agent containing said compound and its preparation method Download PDFInfo
- Publication number
- CN100343231C CN100343231C CNB031201636A CN03120163A CN100343231C CN 100343231 C CN100343231 C CN 100343231C CN B031201636 A CNB031201636 A CN B031201636A CN 03120163 A CN03120163 A CN 03120163A CN 100343231 C CN100343231 C CN 100343231C
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- China
- Prior art keywords
- pyrrolinone
- general formula
- subunit
- hydrogen atom
- expression
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 68
- 239000003086 colorant Substances 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- HMXQIFUGFZEJEO-UHFFFAOYSA-N 1,2-dihydropyrrol-3-one Chemical compound O=C1CNC=C1 HMXQIFUGFZEJEO-UHFFFAOYSA-N 0.000 claims description 77
- 125000003118 aryl group Chemical group 0.000 claims description 29
- -1 carbalkoxy Chemical group 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 125000003282 alkyl amino group Chemical group 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 7
- 150000004056 anthraquinones Chemical class 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 159000000009 barium salts Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 239000000049 pigment Substances 0.000 abstract description 10
- 239000000975 dye Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 4
- 125000004494 ethyl ester group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- JTHGDSIMZGTYIZ-UHFFFAOYSA-N N1C=CC(C1)=O.N1C=CC(C1)=O Chemical compound N1C=CC(C1)=O.N1C=CC(C1)=O JTHGDSIMZGTYIZ-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A bipyrrolinonylidene-type compound is provided which is useful as colorants such as dyes and pigments, or other organic chemical products or intermediates thereof. A method of producing the bipyrrolinonylidene-type compound is also provided, which is suitable for large-scale industrial production with high yield. The bipyrrolinonylidene-type compound is represented by general formula (1). The present invention provides the bipyrrolinonylidene-type compound by oxidizing a pyrrolinone-type compound represented by the general formula (3) in the presence of an anthraquinone-type catalyst.
Description
Technical field
The present invention relates to be applied to two pyrrolinone subunit (bipyrrolinonylidene) compounds and manufacture method thereof in the tinting materials such as dyestuff or pigment.
Background technology
Disclose a kind of will be with formula (a)
Formula (a)
The pyrrolinone (pyrrolinone) of expression is by atmospheric oxidation, and produces the method (with reference to Liebigs Ann.Chem., 702,112～130 (1967)) of two pyrrolinone subunits of representing with formula (b).
Formula (b)
But the yield of the two pyrrolinone subunits that obtain with aforesaid method is lower, is 10～15%, so aforesaid method and be not suitable for the large-scale industrial production of two pyrrolinone subunits.
In addition, low with following formula (b) represented two pyrrolinone subunits to the solvability of water and organic solvent, so be difficult to use as dyestuff, pigment or other organic chemicals or their intermediate.
Summary of the invention
The problem that the present invention need solve is, provide a kind of as tinting materials such as dyestuff, pigment or other organic chemicals or their intermediate and two pyrrolinone subunit compounds of using, and high yield is provided, is suitable for the manufacture method of two pyrrolinone subunit compounds of large-scale industrial production.
Present inventors find, by make the method for pyrrolinone compound atmospheric oxidation with specific catalyst, can produce with high yield and present bright-coloured navy, and can be dissolved in the two pyrrolinone subunit compounds in the various organic solvents, finish the present invention thus.
That is, the present invention is in order to solve above-mentioned problem, and providing can a kind of two pyrrolinone subunit compounds with general formula (1) expression.
General formula (1)
In the formula: Ar
1And Ar
2Represent aryl, R respectively independently
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are that 1～18 alkyl, carbonatoms are 3～18 cycloalkyl or aryl.
In addition, in order to solve above-mentioned problem, provide a kind of, and make method with two pyrrolinone subunit based compounds of general formula (4) expression by the pyrrolinone compound of oxidation in the presence of the anthraquinone series catalysts with general formula (3) expression.
General formula (3)
In the formula: Ar
3Expression aryl, R represent hydrogen atom, halogen atom, cyano group, hydroxyl, alkyl, alkoxyl group, amino, alkylamino, cycloalkyl, cycloalkyloxy, aryl, carbalkoxy, cycloalkoxycarbonyl, formamyl, nitro, carboxyl or sulphonate-base;
General formula (4)
In the formula: Ar
3Expression aryl, R represent hydrogen atom, halogen atom, cyano group, hydroxyl, alkyl, alkoxyl group, amino, alkylamino, cycloalkyl, cycloalkyloxy, aryl, carbalkoxy, cycloalkoxycarbonyl, formamyl, nitro, carboxyl or sulphonate-base.
Two pyrrolinone subunit dicarboxylic acid based compounds of the above-mentioned formula of usefulness of the present invention (1) expression are because present bright-coloured navy, so can be directly can be used as pigment and use as the metal-salt of dyestuff use or two pyrrolinone subunit dicarboxylic acid.
In addition, manufacturing method according to the invention can produce the two pyrrolinone subunit based compounds with above-mentioned formula (4) expression by the simple method of atmospheric oxidation pyrrolinone compound in the presence of the anthraquinone series catalysts.The represented two pyrrolinone subunit based compounds of the above-mentioned general formula of usefulness (4) that obtain by manufacture method of the present invention, because have carboxyl or ester bond, so compare with two pyrrolinone subunits in the past, can be dissolved in a lot of organic solvents, so as dyestuff, pigment or other organic chemicals or their intermediate and use.
Embodiment
Describe the present invention below in detail.
In two pyrrolinone subunit based compounds of the above-mentioned general formula of the usefulness of Shi Yonging (1) expression in the present invention, Ar
1And Ar
2Represent aryl respectively independently.As above-mentioned aryl can exemplified by phenyl, fragrant cyclic group such as naphthyl, anthryl, phenanthryl, pyrenyl, xenyl; Aromatic heterocycles such as pyrryl, pyrazolyl, imidazolyl, pyridyl, pyrimidyl, pyrazinyl, indyl, quinolyl, carbazyl, furyl, thiazolyl.
In addition, above-mentioned aromatic nucleus can also have substituting group.As substituting group, can exemplify hydrogen atom, halogen atom, cyano group, hydroxyl, alkyl, amino, alkylamino, alkoxyl group, carbalkoxy, formamyl, nitro, sulfonic group or sulphonate-base etc.In these substituting groups, it is desirable to halogen atom or sulfonic group.When substituting group is halogen, the chemical stability of two pyrrolinone subunit dicarboxylic acid derivatives (A) improves easily, in addition, when substituting group was sulfonic group or metal organic sulfonate base, two pyrrolinone subunit dicarboxylic acid derivatives (A) improved easily in the solvability of water or organic solvent.
In addition, when above-mentioned aromatic nucleus was replaced by a plurality of halogen atoms, halogen atom can be the same or different.When halogen atom was chlorine atom or bromine atoms, the chemical stability of two pyrrolinone subunit dicarboxylic acid derivatives (A) improved easily, so be ideal.
In addition, in the above-mentioned general formula (1), R
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are that 1～18 alkyl, carbonatoms are 3～18 cycloalkyl or aryl.Wherein, R
1And R
2Represent independently that respectively hydrogen atom or carbonatoms are that 1～18 alkyl is an ideal.As above-mentioned carbonatoms is 1～18 alkyl, can exemplified by methyl, cycloalkyl such as alkyl, cyclohexyl such as ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, Octadecane base.Wherein, R
1And R
2When representing independently that respectively carbonatoms is 1～18 alkyl, improve thermostability easily, so ideal with two pyrrolinone subunit compounds of general formula (1) expression.
In two pyrrolinone subunit compounds with general formula (1) expression, it is desirable to two pyrrolinone subunit compounds with general formula (2) expression.
General formula (2)
In the formula: X
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8, X
9And X
10Represent hydrogen atom, halogen atom, cyano group, hydroxyl, alkyl, amino, alkylamino, alkoxyl group, aryl, carbalkoxy, cyclo alkoxy carbonyl, formamyl, nitro, sulfonic group or sulphonate-base, R respectively independently
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are that 1～18 alkyl, carbonatoms are 3～18 cycloalkyl or aryl.
The two pyrrolinone subunit compounds that use in the present invention with general formula (1) expression, because have carboxyl or ester bond at intramolecularly, so water and organic solvent are had very high solvability, and because present the tone of Lan Zhizi, so can use itself as dyestuff.In addition, in the compound with general formula (1) expression, because R
1And R
2For the metal-salt of two pyrrolinone subunit based compounds of hydrogen atom in the water insoluble or organic solvent, so can use as pigment.
In the two pyrrolinone subunit based compounds that use among the present invention, R
1And R
2For two pyrrolinone subunit based compounds of hydrogen atom have solvability to water and organic solvent, and introduce various atomic groups, can give the solvability that is fit to its purpose and purposes by making carboxyl produce reaction.
Below explanation, in the two pyrrolinone subunit based compounds that use in the present invention with general formula (1) expression, R
1And R
2Be the metal-salt of the compound of hydrogen atom or the situation of its ester.
The two pyrrolinone subunit based compounds with general formula (1) expression that use among the present invention can be 1 or 2 and atoms metal formation salt in its 2 carboxyls, and the solvability of the metal-salt that generates is subjected to the influence of atoms metal kind very big.When atoms metal was basic metal such as sodium, potassium, metal-salt was water-soluble, but when atoms metal was polyvalent metal such as calcium, barium, aluminium, strontium, metal-salt was water insoluble.The pigment that tinting material of the present invention is used as printing-ink and when using, it is desirable to water insoluble, so use polyvalent metal salts such as calcium, aluminium for well.
Two pyrrolinone subunit based compounds of the general formula that uses in the present invention in addition, (1) expression can be that 1 or 2 in its 2 carboxyls is ester.As ester, can exemplify the ester or the 2-hydroxyethyl ester, 2 of aliphatics monovalent alcohols such as methyl esters, ethyl ester, n-propyl, positive butyl ester, isobutyl ester, just own ester, n-octyl, positive last of the ten Heavenly stems ester, Octadecane ester, the ester of aliphatics multivalence alcohol such as 3-dihydroxyl propyl ester, 4-hydroxyl butyl ester, the own ester of 6-hydroxyl; The ester of benzyl ester, allyl ester, 2-(methacryloyl)-ethyl ester, 2-(pyran oxygen)-unsaturated alcohols such as ethyl ester.Wherein, from considering that as the high angle of the chemical stability of ester group the ester of the ester of fatty alcohol, especially fatty alcohol demonstrates high chemical stability, so desirable.
The two pyrrolinone subunit compounds that use among the present invention are by aryl, Ar
1And Ar
2Chemical structure and the kind of the salifiable atoms metal of shape or the chemical structure of ester, in the color region from indigo plant to the purple, has bright-coloured tone, and, can be widely used in fiber staining agent, printing-ink, colour filter, automotive coating or plastic colorant etc. as tinting material.Of the present invention pair of pyrrolinone subunit dicarboxylic acid derivatives (A) has good tinting strength when using separately, mix colours but also can mix with other tinting material.
The two pyrrolinone subunit compounds that use among the present invention are to obtain by the pyrrolinone based compound with above-mentioned general formula (3) expression is carried out oxidation.In the present invention, can the pyrrolinone based compound with general formula (3) expression be carried out oxidation, and make two pyrrolinone subunit based compounds by in the presence of the anthraquinone series catalysts with above-mentioned general formula (4) expression.
Manufacture method by of the present invention pair of pyrrolinone subunit based compound, with the R in the general formula (3) be carboxyl or carbonatoms be the pyrrolinone based compound of 1～18 carbalkoxy as initial feed, can produce two pyrrolinone subunit based compounds with general formula (1) expression.
In general formula (3) and general formula (4), as using Ar
3Represented aryl can exemplify the group that benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl etc. have aromatic nucleus; Pyrroles, pyrazoles, imidazoles, pyridine, pyrimidine, pyrazine, indoles, quinoline, carbazole, furans, thiazole etc. have the group of heteroaromatic.The aromatic nucleus in the aryl or the number of heteroaromatic are few more, and the two pyrrolinone subunit based compounds that obtain are to the easy more height of the solvability of organic solvent.Aryl can have substituting group.As above-mentioned substituting group, can exemplify halogen atom, cyano group, hydroxyl, alkyl, amino, alkyl amine group, alkoxyl group, carbalkoxy, cycloalkoxycarbonyl, formamyl, nitro, sulfonic group or sulphonate-base etc.Chemical stability height when substituting group is halogen atom, and substituting group is can be with the salifiable sulfonic group of atoms metal shape the time, the two pyrrolinone subunit based compounds that obtain uprise easily to the solvability of water or organic solvent.
In general formula (3) and general formula (4); R represent halogen atom, cyano group, hydroxyl, the amino that can be replaced by alkyl, alkoxyl group, cycloalkyloxy, alkyl, cycloalkyl, aryl, carbalkoxy, cycloalkoxycarbonyl, formamyl, nitro, can with the salifiable carboxyl of atoms metal shape, can with the salifiable sulfonic group of atoms metal shape; when substituting group is cyano group, alkyl, aryl, carbalkoxy, can be with the salifiable carboxyl of atoms metal shape the time, the chemical stability of the two pyrrolinone subunit based compounds that obtain is improved.
In the manufacture method of of the present invention pair of pyrrolinone subunit based compound, as the anthraquinone series catalysts, can exemplify anthraquinone-beta-sulfonic acid sodium or anthraquinone-β, β '-sodium disulfonate etc.The usage quantity of anthraquinone series catalysts, the pyrrolinone based compound with respect to general formula (3) expression it is desirable to 1～50mol%, and that better is 2～30mol%.
Using solvent in the oxidizing reaction of the pyrrolinone based compound of representing with general formula (3) is ideal.As the solvent that can use, for example be alcohols such as aromatic series series solvent, methyl alcohol, ethanol, Virahol, isopropylcarbinol, ethylene glycol monobutyl ether such as nitro benzene,toluene,xylene; Ester classes such as ethyl acetate, butylacetate, 2-ethoxyethyl acetate(EA); Non-proton property such as N-Methyl pyrrolidone polar solvent; The mixed solvents of water and water-miscible organic solvent and water etc. in the presence of the anthraquinone series catalysts, are difficult to the solvent of oxidation.Wherein, the oil of mirbane that the ability of the dissolving pyrrolinone based compound of available general formula (3) expression is high or the mixed solvent of oil of mirbane and other organic solvent are because can access high yield, so desirable.
In the present invention, as oxygenant, can use various oxygenants.Can exemplify superoxide, oxygen, air etc. such as hydrogen peroxide, m-chlorine peroxybenzoic acid, peracetic acid, mistake chloric acid, potassium permanganate particularly.If the use air then has safe, as can to reduce manufacturing cost advantage.Use in the oxidizing reaction of air as oxygenant, the lower limit for the limits of explosion concentration that reduces reaction system can mix rare gas elementes such as nitrogen in air.
In the oxidizing reaction, in order to improve speed of response, can the reacting by heating system, and for oxidizing reaction is carried out equably, the stirring reaction system is an ideal.In the oxidizing reaction of air as oxygenant, 100～250 ℃, it is desirable to 140～230 ℃, better be under 170～210 ℃ the temperature of reaction, fully stir, to reaction system equably air supply be ideal.
Two pyrrolinone subunit based compounds of available general formula (1) expression of using among the present invention are to pass through, and obtain with the method for making two pyrrolinone subunit based compounds of available above-mentioned general formula (4) expression with the pyrrolinone compound of above-mentioned general formula (3) expression as raw material.
Embodiment
Below, by embodiment, illustrate in greater detail the present invention.In addition, short of special explanation, [part] and [%] represents [weight part] and [weight %] respectively.
(embodiment 1)
By with formula (5)
0.75 part in 7.5 parts of pyrrolinone carboxylic acid, ethyl esters, the anthraquinone-beta-sulfonic acid sodium of expression and the mixture of 275 parts of compositions of oil of mirbane in air draught, are heated to 180 ℃ while stirring.After under uniform temp, stirring 1 hour, be cooled to room temperature in the time of stirring.Under reduced pressure remove benzene from dark atroceruleous reaction mixture, add 230 parts hexane in the dark dark blue solid in remaining in reaction vessel, after refluxing while stirring 1 hour, suction filtration is used hexane wash.From re-crystallizing in ethyl acetate, obtaining fusing point is 330 ℃, the visible light maximum absorption wavelength (λ of dimethyl sulfoxide solution
Max) be 6.0 parts of the dark navy crystallizations (yield 80%) of 547nm.The result that IR (infrared spectroscopy) analyzes, NMR (NMR (Nuclear Magnetic Resonance) spectrum) analyzes, EI-MS (electron bombardment mass analysis spectrum) analyzes is carried out in the dark navy crystallization that obtains, obtained following result.
[IR analytical results]
3170cm
-1: the N-H stretching vibration of pyrrolinone cyclic amide-CONH-
2990cm
-1: ethyl ester-COOCH
2CH
3The C-H stretching vibration
1725cm
-1: ethyl ester-COOCH
2CH
3The C=O stretching vibration
1675cm
-1: the C=O stretching vibration of pyrrolinone cyclic amide-CONH-
1245cm
-1: ethyl ester-COOCH
2CH
3CO-OCH
2CH
3Stretching vibration
1105cm
-1: ethyl ester-COOCH
2CH
3The COO-C stretching vibration
[NMR analytical results]
1H-NMR(d6-DMSO)
11.3ppm:2H, the hydrogen of s, pyrrolinone cyclic amide-CONH-
8.1 the hydrogen of～7.5ppm:10H, m, phenyl
4.1ppm:4H, q, ethyl ester-COOCH
2CH
3Methylene radical hydrogen
1.2ppm:6H, t, ethyl ester-COOCH
2CH
3Methyl hydrogen
13C-NMR(d6-DMSO)
168ppm: the carbon of pyrrolinone cyclic amide-CONH-
164ppm: ethyl ester-COOCH
2CH
3Carbonyl carbon
152ppm: the 5th carbon (the carbon C adjacent of pyrrolinone ring with phenyl
6H
5-C)
131～128ppm: the carbon of phenyl
109ppm: the 4th carbon (the carbon C-COOC adjacent of pyrrolinone ring with ester bond
2H
5)
60ppm: ethyl ester-COO-CH
2-mesomethylene carbon
14ppm: ethyl ester-COOCH
2-CH
3Methyl carbon
[EI-MS analytical results]
The result of mass analysis under 110～195 ℃ of DI temperature, detects the molecular ion peak (M of two pyrrolinone subunit dicarboxylic diesters (molecular weight 458)
+).
Can confirm that by The above results this compound is to have with formula (6)
Two pyrrolinone subunit dicarboxylic diesters of the chemical structure of expression.
The two pyrrolinone subunit dicarboxylic diesters that obtain dissolve in N, and dinethylformamide and methyl-sulphoxide are slightly soluble in ethanol.
(embodiment 2)
7.5 parts of pyrrolinone carboxylic acid, ethyl esters, anthraquinone-1 by following formula (5) expression, the mixture of 275 parts in 0.75 part of 5-sodium sulfonate and oil of mirbane and 20 parts of compositions of dimethylbenzene in air draught, is heated to 190 ℃ while stirring.With デ イ ソ シ ユ Network ト ラ Star プ, outside reaction system, discharge the water that generates with reaction.After under uniform temp, stirring 1 hour, be cooled to room temperature while stirring, join in 1000 parts of hexanes, stirred 30 minutes under the room temperature, then filtering-depositing containing dark dark blue sedimentary reaction mixture.Successively, obtain dark atroceruleous resultant of reaction, then this resultant of reaction is dispersed in 1500 parts in the water, at room temperature stirred 1 hour with hexane, ethyl acetate washing and filtering thing.Filter, once more resultant of reaction is dispersed in 1700 parts in the water after the washing, at room temperature stirred 2 hours.After filtering, washing, then the water thorough washing carries out drying then, obtains 5.6 parts of solids (yield 75%).From the result that dark navy solid infrared spectroscopic analysis, NMR are analyzed and EI-MS analyzes, two pyrrolinone subunit dicarboxylic diesters that the usefulness formula of confirming to obtain among above-mentioned dark navy solid and the embodiment 1 (6) is represented have identical chemical structure.
In addition, above-mentioned dark navy solid results of elemental analyses shows that in the error at measurment scope (± 0.3%) that allows, this result is consistent with the ultimate analysis theoretical value of two pyrrolinone subunit dicarboxylic diesters of representing with formula (6).
[determination of elemental analysis result]
Measured value: C=68.05% H=4.82% N=6.03%
Theoretical value: C=68.11% H=4.84% N=6.11%
(embodiment 3)
To in embodiment 2, obtain, have with 4.6 parts of two pyrrolinone subunit diethyl dicarboxylates of the chemical structure of formula (6) expression and join in 350 parts of 14% aqueous sodium hydroxide solutions, stir on the limit, the while was 50 ℃ of following hydrolysis 1 hour.With the red tan solution that obtains ice-cold after, filter and obtain black purple resolution of precipitate in 1L water, ice-cold stirring, add simultaneously 35% hydrochloric acid about 13 parts neutralize after, add hydrochloric acid again, the pH that adjusts solution is 1.The black dark brown precipitation that the suction filtration acid out goes out, drying is carried out in washing behind the washing with acetone, obtain the visible light maximum absorption wavelength (λ of dimethyl sulfoxide solution
Max) be 0.8 part of the bright-coloured dark navy solid (yield 20%) of 567nm.Analyze above-mentioned navy solid result by IR (infrared spectroscopy) analysis, NMR (NMR (Nuclear Magnetic Resonance) spectrum), obtain following result.
[IR analytical results]
3420cm
-1: the N-H stretching vibration of pyrrolinone cyclic amide-CONH-
3150cm
-1: the O-H stretching vibration of carboxyl-COOH
3060cm
-1: phenyl-C
6H
5The C-H stretching vibration
1765cm
-1: the C=O stretching vibration of carboxyl-COOH
1680cm
-1: the C=O stretching vibration of pyrrolinone cyclic amide-CONH-
1255cm
-1: the CO-OH stretching vibration of carboxyl-COOH
[NMR analytical results]
1H-NMR(d6-DMSO)
13.5ppm:2H, the hydrogen of s, carboxyl-COOH
10.8ppm:2H, the hydrogen of s, pyrrolinone cyclic amide-CONH-
8.3 the hydrogen of～6.9ppm:10H, m, phenyl
Can confirm that by The above results this compound has with formula (7)
The chemical structure of two pyrrolinone subunit dicarboxylic acid of expression.
(embodiment 4)
To in embodiment 3, obtain, have with 0.8 part of the pyrrolinone dicarboxylic acid of the chemical structure of formula (7) expression and join in 100 parts of 20% aqueous sodium hydroxide solutions, stir, add 95 parts of methyl alcohol again.Add hydrochloric acid in the red solution that obtains, adjusting pH is 9, adds 4 parts in Tai-Ace S 150 14～18 hydrates then, the black navy precipitation that suction filtration is separated out, and washing, washing with acetone, drying obtains dark navy solid.
The navy solid that obtains among the embodiment 4 is insoluble in hexane, toluene, Virahol and the water, presents bright-coloured dark blue purple, is suitable as printing-ink pigment.
Above-mentioned navy solid is carried out IR (infrared analysis) and heat is analyzed, the residue that obtains in the heat analysis is carried out the result of x-ray fluorescence analysis and powder X-ray X-ray analysis X, obtain following result.
[IR analytical results]
3430cm
-1: the N-H stretching vibration of pyrrolinone cyclic amide-CONH-
1680cm
-1: the C=O stretching vibration of pyrrolinone cyclic amide-CONH-
1055cm
-1: the CO-OAl stretching vibration of carboxylate group-COOAl
[hot analytical results]
Organic composition 95.4%, inorganic components 4.6%.
[x-ray fluorescence analysis result]
The X ray intensity of detected principal element and ratio (%)
Al 4.15(47％)、Na 0.35(22％)、
Si 0.53(12％)、Ca 0.67(6％)
Judge Al salt and Na salt with 47% from the result of x-ray fluorescence analysis: 22%=1.74%: 0.96mol% 2mol: 1mol exists.
[powder X-ray X-ray analysis X result]
Confirm θ/2 θ=21 °, 30 °, 33 °, 35 ° diffraction peaks.Whole and the NaAlO in these peaks
2Main diffraction peak unanimity.
From above result, except Al salt structure, also there is the sodium salt structure in judgement in the navy solid of embodiment 4.
According to the navy solid x-ray fluorescence analysis result who obtains among the embodiment 4, the ratio of Al and Na is 2: 1, and as prerequisite, the divalent negatively charged ion [molecular formula=(C of two pyrrolinone subunit dicarboxylic acid
22H
12O
6N
2)
2-] consistent with hot analytical results with the ratio of Al and Na.Its result, judging has 7 (C in each molecule of navy solid
22H
12O
6N
2)
2-, 4 Al, 2 Na.Be that the navy solid that obtains among the embodiment 4 is with structural formula [(C
22H
12O
6N
2)
2-]
7(Al
3+)
4, (Na
+)
2The pigment lake of expression.
Claims (13)
1, a kind of pair of pyrrolinone subunit based compound is characterized in that with following general formula (1) expression, general formula (1)
In the formula: Ar
1And Ar
2Represent fragrant cyclic group, R respectively independently
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are that 1～18 alkyl, carbonatoms are 3～18 cycloalkyl or aryl.
2, according to claim 1 pair of pyrrolinone subunit based compound, wherein above-mentioned pair of pyrrolinone subunit based compound is with general formula (2) expression
General formula (2)
In the formula: X
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8, X
9And X
10Represent hydrogen atom, halogen atom, cyano group, hydroxyl, alkyl, amino, alkylamino, alkoxyl group, aryl, carbalkoxy, cyclo alkoxy carbonyl, formamyl, nitro, sulfonic group or sulphonate-base, R respectively independently
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are that 1～18 alkyl, carbonatoms are 3～18 cycloalkyl or aryl.
3, according to claim 2 pair of pyrrolinone subunit based compound, wherein in above-mentioned general formula (2), X
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8, X
9And X
10Represent hydrogen atom or halogen atom respectively independently, and R
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are 1～18 alkyl.
4, according to claim 2 couple of pyrrolinone subunit based compound, wherein X
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8, X
9And X
10All expression hydrogen atoms, and R
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are 1～8 alkyl.
5, a kind of tinting material is characterized in that, comprises from two pyrrolinone subunit based compounds and the described general formula of claim 1 (1) with the described general formula of claim 1 (1) expression R
1And R
2Two pyrrolinone subunit based compounds of selecting in two pyrrolinone subunit based compound metal-salts for hydrogen atom.
6, tinting material according to claim 5, comprising from two pyrrolinone subunit based compounds and the described general formula of claim 2 (2) with the described general formula of claim 2 (2) expression, R
1And R
2Two pyrrolinone subunit based compounds of selecting in two pyrrolinone subunit based compound metal-salts for hydrogen atom.
7, tinting material according to claim 6, wherein X
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8, X
9And X
10Represent hydrogen atom or halogen atom respectively independently, and R
1And R
2Represent independently that respectively hydrogen atom, carbonatoms are 1～18 alkyl.
8, tinting material according to claim 6, wherein X
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8, X
9And X
10All expression hydrogen atoms, and R
1And R
2Represent independently that respectively hydrogen atom or carbonatoms are 1～8 alkyl.
9, according to any described tinting material of claim 5～8, the metal-salt of wherein above-mentioned pair of pyrrolinone subunit based compound is an an alkali metal salt.
10, according to any described tinting material of claim 5～8, the metal-salt of wherein above-mentioned pair of pyrrolinone subunit based compound is sodium salt or sylvite.
11, according to any described tinting material of claim 5～8, the metal-salt of wherein above-mentioned pair of pyrrolinone subunit based compound is a polyvalent metal salt.
12, according to any described tinting material of claim 5～8, the metal-salt of wherein above-mentioned pair of pyrrolinone subunit based compound is calcium salt, barium salt or aluminium salt.
13, the manufacture method of a kind of pair of pyrrolinone subunit by the compound of oxidation in the presence of the anthraquinone series catalysts with general formula (3) expression, and is made two pyrrolinone subunit based compounds of representing with general formula (4),
General formula (3)
In the formula: Ar
3The expression aryl, R represents hydrogen atom, halogen atom, cyano group, hydroxyl, alkyl, alkoxyl group, amino, alkylamino, cycloalkyl, cycloalkyloxy, aryl, carbalkoxy, cyclo alkoxy carbonyl, formamyl, nitro, carboxyl or sulfonic group;
General formula (4)
In the formula: Ar
3Expression aryl, R represent hydrogen atom, halogen atom, cyano group, hydroxyl, alkyl, alkoxyl group, amino, alkylamino, cycloalkyl, cycloalkyloxy, aryl, carbalkoxy, cyclo alkoxy carbonyl, formamyl, nitro, carboxyl or sulfonic group.
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| Country | Link |
|---|---|
| US (1) | US6740153B2 (en) |
| EP (1) | EP1344778B1 (en) |
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2003
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- 2003-03-11 US US10/384,707 patent/US6740153B2/en not_active Expired - Fee Related
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- 2003-03-11 CN CNB031201636A patent/CN100343231C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Isoindigo dyes of the pyrrole series TREIBS,ALFRED ET AL,JUSTUS LIEBIGS ANN. CHEM.,Vol.702 1967 * |
| Methylenedeoxybenzoins. VIII. The reactionofgamma.-oxoacids with ammonium acetate FIESSELMANN,HANS ET AL,CHEMISCHE BERICHTE,Vol.91 1958 * |
| Synthetic studies related to diketopyrrolopyrrole(DPP)pigments. MORTON,COLIN J. H. ET AL,TETRAHEDRON,Vol.58 No.27 2002 * |
| Trikendiol,an unusual red pigment from the spongeTrikentrion loeve,anti-HIV-1 metabolite LOUKACI,ALI ET AL,TETRAHEDRON LETTERS,Vol.35 No.37 1994 * |
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| CN1443757A (en) | 2003-09-24 |
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| US6740153B2 (en) | 2004-05-25 |
| EP1344778B1 (en) | 2008-09-03 |
| DE60323288D1 (en) | 2008-10-16 |
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